WO2005023952A1 - Vulcanizable adhesive composition - Google Patents

Vulcanizable adhesive composition Download PDF

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Publication number
WO2005023952A1
WO2005023952A1 PCT/JP2003/010829 JP0310829W WO2005023952A1 WO 2005023952 A1 WO2005023952 A1 WO 2005023952A1 JP 0310829 W JP0310829 W JP 0310829W WO 2005023952 A1 WO2005023952 A1 WO 2005023952A1
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Prior art keywords
weight
parts
rubber
resin
adhesive composition
Prior art date
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PCT/JP2003/010829
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French (fr)
Japanese (ja)
Inventor
Kiyofumi Fukasawa
Tomohiro Kaise
Original Assignee
Nok Corporation
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Publication date
Application filed by Nok Corporation filed Critical Nok Corporation
Priority to PCT/JP2003/010829 priority Critical patent/WO2005023952A1/en
Priority to CNB038247003A priority patent/CN1326965C/en
Priority to EP20030816006 priority patent/EP1659161B1/en
Priority to US10/506,490 priority patent/US7247388B2/en
Priority to AU2003261749A priority patent/AU2003261749A1/en
Publication of WO2005023952A1 publication Critical patent/WO2005023952A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C09J123/286—Chlorinated polyethylene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • C09J165/04—Polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/286—Chlorinated polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/12—Homopolymers or copolymers not provided for in C08L2666/06 - C08L2666/10
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C08L65/04—Polyxylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31688—Next to aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]

Definitions

  • the present invention relates to a vulcanized adhesive composition. More particularly, the present invention relates to a vulcanized adhesive composition which is effectively used for vulcanization bonding of metal and (hydrogen) nitrile rubber.
  • a chlorinated rubber or novolac phenolic resin adhesive is used for adhesion between metal and nitrile rubber (NBR).
  • NBR nitrile rubber
  • a chlorinated rubber or novolac phenolic resin adhesive is used for adhesion between metal and nitrile rubber (NBR).
  • the chlorinated rubber adhesive does not have adhesion to metal, it is necessary to separately apply a phenol-based primer, and the viscosity is high and coating workability is poor, and further, In order to obtain good adhesion, a film thickness of at least 5 ⁇ or more is required, and there is a problem that it becomes an obstacle in the case of parts requiring dimensional accuracy and inlaid parts.
  • novolak phenolic resin adhesive the applicable rubber range is narrow because it adheres only to (hydrogen) NBR with a content of 30% to 40%, and hexamethylenediamine as a curing agent. Due to the inclusion, gas was generated during drying and baking, and there was a problem when contaminating the inside of the dryer. Furthermore, all these adhesives have poor resistance to various refrigerants such as fluorocarbon gas, water, and ⁇ G (polyalkylene glycol), and their application to refrigerant seals is difficult.
  • refrigerants such as fluorocarbon gas, water, and ⁇ G (polyalkylene glycol
  • a vulcanized adhesive composition comprising, as essential components, resol type phenol resin, unvulcanized NBR, chlorinated polyethylene, etc. -No. 306340, No. 8-302323).
  • these vulcanized adhesive compositions are used, good adhesion can be obtained for (hydrogenated) NBRs having a ditrile content of less than 30.
  • (hydrogenated) NBRs having a ditrile content of 40 or more Although it still does not show good adhesion and resistance to various refrigerants is superior to the above-mentioned chlorinated rubber-based or phenol-based adhesive, it does not satisfy the currently required level.
  • the object of the present invention is a vulcanized adhesive composition for use in the vulcanization bonding of metal and (hydrogenated) -tolyl rubber, which is effective for (hydrogenated) tolyl rubber having a tolyl content of 18 to 48%. It is another object of the present invention to provide a material which can be used for the purpose of suppressing the decrease in adhesion even when it is immersed in various refrigerants such as fluorocarbon gas, polyalkylene glycol or water for a long time.
  • the object of the present invention is as follows: 100 parts by weight of phenol xylerin resin or phenol biphenyl resin, 10 to 1000 parts by weight of resol type phenol resin, 0 to 1000 parts by weight of nopolac type phenol resin, 10 to 1000 parts by weight of unvulcanized 2 tolyl rubber This is achieved by a vulcanized adhesive composition comprising parts by weight and 10 to 500 parts by weight of chlorinated polyethylene.
  • the phenol xylerin resin is a condensation reaction product of 1,4-bis (alkoxymethyl) benzene and phenol or a phenol derivative having at least one methylol group at the 2, 4-position, and in practice Commercially available products, such as Meiwa Kasei Co., Ltd. MR-7800 can be used as it is.
  • pheno-biphenyl resin is a condensation reaction product of 4, 4-bis (alkoxymethyl) biphenyl and phenol or a phenol derivative having at least one methylol group in the 2, 4 -position thereof.
  • commercially available products such as Meiwa Kasei Co., Ltd. MR-7850 can be used as it is.
  • phenol resin resol type phenol resin or resin obtained by using nopolac type phenol resin in combination with phenol resin is used.
  • resol type phenol resin phenols and formaldehyde are added in the presence of an alkaline catalyst.
  • phenololes obtained by condensation reaction are used as phenolols, with respect to phenol hydroxyl groups such as phenol, p-cresol, in-cresol, p-third pentylphenol and the like.
  • Phenyls having 2 or 3 substitutable nuclear hydrogen atoms at-position or a mixture thereof are used, and as the alkaline catalyst, ammonia, alkali metal hydroxide, magnesium hydroxide etc. are used.
  • m_cresol and p Mixtures of cresol and those prepared from formaldehyde are used.
  • the novolac phenol resin a resin obtained by condensation reaction of phenols and formaldehyde in the presence of an acid catalyst is used.
  • phenols 2 or 3 substitution at the 0-position and / or P-position with respect to phenol hydroxyl groups such as phenol, p-cresol, ra-cresolol, p-third ptyylphenol etc.
  • a phenol having a possible nuclear hydrogen atom or a mixture of these is used, and as an acid catalyst, oxalic acid, hydrochloric acid, maleic acid etc. are used.
  • the unvulcanized 2 tolyl rubber As the unvulcanized 2 tolyl rubber, it is a commercially available product with a very high 2 tolyl content (more than 43% of 2 tolyl content), a high tolyl content (36 to 42% of the same), and a middle to high toly content (31 to 35% of the same).
  • a variety of tolyl rubbers having a medium toltrile content (25 to 30% the same) and a low-tolyl content (not more than 24% on the same) may optionally be used, but ones having a medium to high content are preferable.
  • chlorinated polyethylene preferably, a highly chlorinated type having a chlorine content of about 60 to 70% is used.
  • Each of the above components is about 10 to 1000 parts by weight, preferably about 20 to 400 parts by weight, of a novolac phenol resin, based on 100 parts by weight of phenol xylerin resin or phenol biphenyl resin.
  • 0 to 1000 parts by weight preferably 0 to 100 parts by weight, 10 to 1000 parts by weight of uncured -tolyl rubber, preferably 20 to 300 parts by weight, and 10 to 500 parts by weight of chlorinated polyethylene, preferably 10 to 10 parts by weight It is used in a proportion of 200 parts by weight.
  • the ratio of resole phenolic resin or this to nopolac phenolic resin is higher than this range, the adhesion durability to fluorocarbons or water will be reduced, while if it is used at a lower ratio, it will be different from the initial metal surface. Adhesion will be reduced. In addition, if unvulcanized-tolyl rubber is used in a larger proportion, adhesion to the metal surface will be reduced, and the viscosity increase will be large, causing problems in the coating operation, while using in a smaller proportion. If so, the compatibility with the tolyl rubber to be adhered is reduced, and adhesion failure will occur.
  • chlorinated polyethylene is used at a higher proportion than this, the adhesive phase becomes brittle and leads to a decrease in strength, while if it is used at a lower proportion, adhesion is poor due to a decrease in reactivity with rubber. Become.
  • a vulcanized adhesive composition containing each of these components as an essential component can be prepared by adding each component to a ketone such as methyl ethyl ketone or methyl isobutyl ketone or an organic solvent such as toluene or an aromatic hydrocarbon such as xylene alone or a mixed solvent It is prepared as a liquid by dissolving it so that its concentration will be 3 to 10% by weight.
  • a ketone such as methyl ethyl ketone or methyl isobutyl ketone
  • an organic solvent such as toluene or an aromatic hydrocarbon such as xylene alone or a mixed solvent
  • Vulcanization bonding using a vulcanized adhesive composition is as follows: Vulcanization: The adhesive composition is a metal such as mild steel, stainless steel, aluminum, aluminum die cast, brass, zinc, etc. This is coated on a metal plate, air-dried at room temperature, and then dried at about 100 to 200 ° C. for about 5 to 30 minutes, and the uncured (hydrogenated) nitrile rubber composition is stored there. Bonding, (Hydrogenation) Nit It is carried out by pressure vulcanization at about 150 to 200 ° C., which is the vulcanization temperature of rill rubber. BEST MODE FOR CARRYING OUT THE INVENTION
  • the unit is part by weight, and the value in Katsuko shows the solid part by weight.
  • Phenyl xylerin resin 143 (100) (Meiwa Chemical Products MR-7800 solid content 70%)
  • Phenyl xylerin resin (MR-7800) 143 (100) Taresol modified nopolac type phenolic resin 20 (8) (Dainippon Ink and Chemicals, Inc. KA-1053L solid content 40%)
  • Resole type fatty acid resin (AF-2639 L) 53 (32) Unvulcanized-Tolyl rubber (N-237) 40 Chlorinated polyethylene (Z-200) 20 Methyl ethyl ketone 1862 Toluene 1862
  • AF-2639 L Resole type fatty acid resin
  • N-237 Unvulcanized-Tolyl rubber
  • Z-200 Chlorinated polyethylene
  • Resole-type phenolic resin (AF-2639 L) 67 (40) Unvulcanized-Tolyl rubber (N-237) 40 Chlorinated polyethylene (Z- 200) 20 Methinoretinoleketone 1865
  • Phenol biphenyl resin MR-7851
  • 143 100
  • Cresol-modified novolak type phenolic resin K-1053L
  • AF-2639L Resol type phenolic resin
  • N Unvulcanized Nitryl rubber
  • Z- 200 Chlorinated polyethylene
  • Methyl ethinole ketone 1862
  • Resole type phenol resin (AF-2639L) 167 (100) Uncured 2 tolyl rubber (N-237) 28 Chlorinated polyethylene (Z- 200) 14 Methyl ethyl ketone 916 Toluene 916 Comparative example 2
  • Unvulcanized nitril rubber (N-237) 40 Chlorinated polyethylene (Z- 200) 20 Methinouretinole ketone 1867 Tonorene 1867 Comparative example 3
  • Cresol-modified novolak-type funinol resin (KA-1053L) 250 (100) resol-type fatty acid resin (AF-2639L) 167 (100) unvulcanized nitril rubber (N-237) 58 chlorinated polyethylene (Z-200) 29 Methionine ethyl ketone 2618 toluene 2618 Comparative Example 4.
  • Chlorinated rubber-based adhesive (load-free paste product Chemlock 252X)
  • the vulcanized adhesive compositions of Examples 1 to 4 and Comparative Examples 1 to 4 comprising the above components were coated on a zinc phosphate-treated mild steel sheet. After coating and air-drying at room temperature for 10 minutes, baking was performed at a baking temperature of 150 ° C. for 10 minutes. Unvulcanized hydrogenated nitrile rubber compounds (units are parts by weight) of the following combination examples 1 to 3 are joined to these vulcanized adhesive-baked soft steel plates, and a pressure of 80 ° C. for 6 minutes is applied. Sulfurization took place.
  • Initial adhesion test of the obtained vulcanized adhesive Testing Water resistance test, PAG resistance test, C Freon resistance test c
  • a sample obtained by pressure-vulcanization molding a 5 ⁇ -thick rubber sheet is placed in a pressure vessel, fluorocarbon gas (R134a) is injected therein, and the sample is left for 24 hours under an environment of 40 ° C. And heated in a 150 ° C oven for 1 hour, at which time the number of fluorocarbon gas bubbles generated at the bonding interface was determined.
  • fluorocarbon gas R134a
  • HNBR (Nippon Zeon Products Zetpol 2020; CN 36%) 100 100
  • Adhesive strength (N / mm) 18. 5 18. 5 18. 5 18. 5--18. 5 10. 1 Rubber residual ratio (o / 0 ) 100 100 100 100--100 0
  • Adhesive strength 17. 5 17. 5 17. 5 17. 5--17. 5 16. 5 Residual rubber percentage (%) 100 100 100 100 1-100 80

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A vulcanizable adhesive composition which comprises 100 parts by weight of a phenol-xylylene resin or phenol-biphenyl resin, 10 to 1,000 parts by weight of a resol resin, 0 to 1,000 parts by weight of a phenolic novolak, 10 to 1,000 parts by weight of a green nitrile rubber, and 10 to 500 parts by weight of chlorinated polyethylene. This vulcanizable adhesive composition is effectively applicable to (hydrogenated) nitrile rubbers having a nitrile content of 18 to 48%. It is prevented from decreasing in adhesiveness even when immersed for long in various refrigerants such as a fluorocarbon gas, polyalkylene glycol, and water.

Description

明 細 書 加硫接着剤組成物 技術分野  Description Vulcanized adhesive composition Technical field
本発明は、 加硫接着剤組成物に関する。 更に詳しくは、 金属と（水素 ィ匕）二トリルゴムとの加硫接着などに有効に用いられる加硫接着剤組成 物に関する。 背景技術  The present invention relates to a vulcanized adhesive composition. More particularly, the present invention relates to a vulcanized adhesive composition which is effectively used for vulcanization bonding of metal and (hydrogen) nitrile rubber. Background art
金属と二トリルゴム（NBR)との接着には、 塩化ゴム系またはノボラッ ク型フエノール樹脂系接着剤が用いられている。 この内、 塩化ゴム系接 着剤については金属との接着性がないため、 別にフヱノール系の下塗り 剤を塗布しておくことが必要であり、 また高粘度であって塗布作業性が 悪く、 さらに良好な接着性を得るためには少なくとも 5 μ ηι以上の膜厚が 必要で、 寸法精度の必要な部品や嵌め込み部品などの場合に障害となる といった問題があった。 一方、 ノボラック型フエノール樹脂系接着剤の 場合、 二トリル含有量が 30〜40%の（水素ィヒ） NBRにしか接着しないため 適用ゴム範囲が狭く、 また硬化剤としてへキサメチレンジァミンを含有 するため、 乾燥、 焼付け時にガスが発生し、 乾燥器内を汚染するといつ た問題があった。 さらに、 これらいずれ接着剤も、 フロンガス、 水、 ΡΑ G (ポリアルキレンダリ コール）などの各種冷媒への耐性が悪く、 冷媒用 シールへの適用が困難であつた。  For adhesion between metal and nitrile rubber (NBR), a chlorinated rubber or novolac phenolic resin adhesive is used. Among them, since the chlorinated rubber adhesive does not have adhesion to metal, it is necessary to separately apply a phenol-based primer, and the viscosity is high and coating workability is poor, and further, In order to obtain good adhesion, a film thickness of at least 5 μι or more is required, and there is a problem that it becomes an obstacle in the case of parts requiring dimensional accuracy and inlaid parts. On the other hand, in the case of novolak phenolic resin adhesive, the applicable rubber range is narrow because it adheres only to (hydrogen) NBR with a content of 30% to 40%, and hexamethylenediamine as a curing agent. Due to the inclusion, gas was generated during drying and baking, and there was a problem when contaminating the inside of the dryer. Furthermore, all these adhesives have poor resistance to various refrigerants such as fluorocarbon gas, water, and ΡΑG (polyalkylene glycol), and their application to refrigerant seals is difficult.
かかる問題点を解決すべく、 本出願人は先にレゾール型フヱノール樹 脂、 未加硫 NBRおよび塩素化ポリエチレンなどを必須成分とする加硫接 着剤組成物を提案している（特開平 6- 306340号公報、 同 8- 302323号公報)。 しかしながら、 これらの加硫接着剤組成物を用いた場合、 二トリル含量 30未満の（水素化） NBRについては、 良好な接着性が得られるものの、 二 トリル含量 40以上の（水素化） NBRについては、 なお良好な接着性を示す ものではなく、 また各種冷媒への耐性は上記塩化ゴム系またはフエノー ル系接着剤よりもすぐれてはいるものの、 現在要求されているレベルを 満足させるものではなかった。 発明の開示 In order to solve such problems, the present applicant has previously proposed a vulcanized adhesive composition comprising, as essential components, resol type phenol resin, unvulcanized NBR, chlorinated polyethylene, etc. -No. 306340, No. 8-302323). However, when these vulcanized adhesive compositions are used, good adhesion can be obtained for (hydrogenated) NBRs having a ditrile content of less than 30. However, for (hydrogenated) NBRs having a ditrile content of 40 or more Although it still does not show good adhesion and resistance to various refrigerants is superior to the above-mentioned chlorinated rubber-based or phenol-based adhesive, it does not satisfy the currently required level. The Disclosure of the invention
本発明の目的は、 金属と（水素化） -トリルゴムとの加硫接着に用いら れる加硫接着剤組成物であって、 二トリル含量が 18〜48%の（水素化） - トリルゴムに有効に使用され、 さらにフロンガス、 ポリアルキレンダリ コールまたは水などの各種冷媒に長時間浸せきした場合にもその接着性 の低下が抑えられるものを提供することにある。  The object of the present invention is a vulcanized adhesive composition for use in the vulcanization bonding of metal and (hydrogenated) -tolyl rubber, which is effective for (hydrogenated) tolyl rubber having a tolyl content of 18 to 48%. It is another object of the present invention to provide a material which can be used for the purpose of suppressing the decrease in adhesion even when it is immersed in various refrigerants such as fluorocarbon gas, polyalkylene glycol or water for a long time.
かかる本発明の目的は、 フエノールキシレリン榭脂またはフエノール ビフヱニル樹脂 100重量部、 レゾール型フヱノール樹脂 10〜1000重量部、 ノポラック型フエノール樹脂 0〜； 1000重量部、 未加硫の二トリルゴム 10 〜1000重量部および塩素化ポリエチレン 10〜500重量部を含有してなる 加硫接着剤組成物によって達成される。  The object of the present invention is as follows: 100 parts by weight of phenol xylerin resin or phenol biphenyl resin, 10 to 1000 parts by weight of resol type phenol resin, 0 to 1000 parts by weight of nopolac type phenol resin, 10 to 1000 parts by weight of unvulcanized 2 tolyl rubber This is achieved by a vulcanized adhesive composition comprising parts by weight and 10 to 500 parts by weight of chlorinated polyethylene.
フエノールキシレリン樹脂は、 1, 4 -ビス（アルコキシメチル）ベンゼン とフエノールまたはその 2， 4 -位に少なくとも 1個のメチロール基を有す るフエノール誘導体との縮重合反応物であり、 実際には市販品、 例えば 明和化成製品 MR-7800等をそのまま用いることができる。 また、 フエノ 一ルビフエ-ル樹脂は、 4， 4 -ビス（アルコキシメチル）ビフエ二ルとフ ェノールまたはその 2， 4 -位に少なくとも 1個のメチロール基を有するフ ノール誘導体との縮重合反応物であり、 実際には市販品、 例えば明和 化成製品 MR- 7850等をそのまま使用することができる。 フエノール樹脂としては、 レゾール型フエノ^"ル樹脂またはこれにノ ポラック型フエノール樹脂を併用したものが用いられる。 レゾール型フ エノール榭脂としては、 フエノール類とホルムアルデヒドとをアルカリ 性触媒の存在下で縮合反応させることによって得られものが用いられる。 この際フエノーノレ類としては、 フエノール、 p-クレゾール、 in-クレゾ一 ル、 p-第 3プチルフヱノール等のフエノール水酸基に対して。 -位および /または P-位に 2個または 3個の置換可能な核水素原子を有するフエノー ル類またはこれらの混合物等が用いられ、 またアルカリ性触媒としては、 アンモニア、 アルカリ金属水酸化物、 水酸化マグネシウム等が用いられ る。 これらのレゾール型フヱノール樹脂のうち、 好ましくは m_クレゾ一 ルおよび p -クレゾールの混合物とホルムァルデヒドから製造されたもの が用いられる。 The phenol xylerin resin is a condensation reaction product of 1,4-bis (alkoxymethyl) benzene and phenol or a phenol derivative having at least one methylol group at the 2, 4-position, and in practice Commercially available products, such as Meiwa Kasei Co., Ltd. MR-7800 can be used as it is. In addition, pheno-biphenyl resin is a condensation reaction product of 4, 4-bis (alkoxymethyl) biphenyl and phenol or a phenol derivative having at least one methylol group in the 2, 4 -position thereof. In fact, commercially available products, such as Meiwa Kasei Co., Ltd. MR-7850 can be used as it is. As phenol resin, resol type phenol resin or resin obtained by using nopolac type phenol resin in combination with phenol resin is used. As resol type phenol resin, phenols and formaldehyde are added in the presence of an alkaline catalyst. In this case, phenololes obtained by condensation reaction are used as phenolols, with respect to phenol hydroxyl groups such as phenol, p-cresol, in-cresol, p-third pentylphenol and the like. Phenyls having 2 or 3 substitutable nuclear hydrogen atoms at-position or a mixture thereof are used, and as the alkaline catalyst, ammonia, alkali metal hydroxide, magnesium hydroxide etc. are used. Of these resole type phenolic resins, preferably m_cresol and p Mixtures of cresol and those prepared from formaldehyde are used.
また、 ノボラック型フエノール樹脂としては、 フエノール類とホルム アルデヒ ドとを酸性触媒の存在下で縮合反応させることによって得られ る樹脂が用いられる。 この際フエノール類としては、 フエノール、 p-ク レゾール、 ra-クレゾーノレ、 p-第 3プチルフエノール等のフエノール水酸 基に対して 0-位および/または P-位に 2個または 3個の置換可能な核水素 原子を有するフエノール類またはこれらの混合物等が用いられ、 また酸 性触媒としては、 しゅう酸、 塩酸、 マレイン酸等が用いられる。  Further, as the novolac phenol resin, a resin obtained by condensation reaction of phenols and formaldehyde in the presence of an acid catalyst is used. Under the present circumstances, as phenols, 2 or 3 substitution at the 0-position and / or P-position with respect to phenol hydroxyl groups such as phenol, p-cresol, ra-cresolol, p-third ptyylphenol etc. A phenol having a possible nuclear hydrogen atom or a mixture of these is used, and as an acid catalyst, oxalic acid, hydrochloric acid, maleic acid etc. are used.
未加硫の二トリルゴムとしては、 市販品である極高二トリル含量（二 トリル含量 43%以上）、 高工トリル含量（同 36〜42%)、 中高工トリル含 量（同 31〜35%)、 中二トリル含量（同 25〜30%)および低-トリル含量 (同 24%以下）の各種二トリルゴムを任意に用いることができるが、 好ま しくは中高-トリル含量のものが使用される。  As the unvulcanized 2 tolyl rubber, it is a commercially available product with a very high 2 tolyl content (more than 43% of 2 tolyl content), a high tolyl content (36 to 42% of the same), and a middle to high toly content (31 to 35% of the same). A variety of tolyl rubbers having a medium toltrile content (25 to 30% the same) and a low-tolyl content (not more than 24% on the same) may optionally be used, but ones having a medium to high content are preferable.
塩素化ポリエチレンとしては、 好ましくは塩素含有量が 60〜70%程度 の高塩素化タイプが用いられる。 以上の各成分は、 フエノールキシレリン樹脂またはフエノールビフヱ -ル榭脂 100重量部に対して、 レゾール型フヱノール樹脂が約 10〜： 1000 重量部、 好ましくは約 20〜400重量部、 ノボラック型フエノール樹脂が 0 〜1000重量部、 好ましくは 0〜100重量部、 未加硫の-トリルゴムが 10〜 1000重量部、 好ましくは 20〜300重量部、 また塩素化ポリエチレンが 10 〜500重量部、 好ましくは 10〜200重量部の割合でそれぞれ用いられる。 レゾール型フエノール樹脂またはこれとノポラック型フエノ一ル榭脂 の割合がこれより多い場合には、 フロンまたは水に対する接着耐久性が 低下し、 一方これより少ない割合で用いられると初期における金属面と の接着性が低下するようになる。 また、 未加硫-トリルゴムがこれより 多い割合で用いられると、 金属面との接着性が低下する他、 粘度上昇が 大きく、 塗布作業に支障をきたすようになり、 一方これより少ない割合 で用いられた場合には、 接着させる二トリル系ゴムとの相溶性が低下し、 接着不良が起こるようになる。 さらに、 塩素化ポリエチレンがこれより ' 多い割合で用いられると、 接着相が脆くなつて、 強度低下につながり、 一方これより少ない割合で用いられると、 ゴムとの反応性低下により接 着性が悪くなる。 As chlorinated polyethylene, preferably, a highly chlorinated type having a chlorine content of about 60 to 70% is used. Each of the above components is about 10 to 1000 parts by weight, preferably about 20 to 400 parts by weight, of a novolac phenol resin, based on 100 parts by weight of phenol xylerin resin or phenol biphenyl resin. 0 to 1000 parts by weight, preferably 0 to 100 parts by weight, 10 to 1000 parts by weight of uncured -tolyl rubber, preferably 20 to 300 parts by weight, and 10 to 500 parts by weight of chlorinated polyethylene, preferably 10 to 10 parts by weight It is used in a proportion of 200 parts by weight. If the ratio of resole phenolic resin or this to nopolac phenolic resin is higher than this range, the adhesion durability to fluorocarbons or water will be reduced, while if it is used at a lower ratio, it will be different from the initial metal surface. Adhesion will be reduced. In addition, if unvulcanized-tolyl rubber is used in a larger proportion, adhesion to the metal surface will be reduced, and the viscosity increase will be large, causing problems in the coating operation, while using in a smaller proportion. If so, the compatibility with the tolyl rubber to be adhered is reduced, and adhesion failure will occur. Furthermore, if chlorinated polyethylene is used at a higher proportion than this, the adhesive phase becomes brittle and leads to a decrease in strength, while if it is used at a lower proportion, adhesion is poor due to a decrease in reactivity with rubber. Become.
これらの各成分を必須成分とする加硫接着剤組成物は、 各成分をメチ ルェチルケトン、 メチルイソブチルケトン等のケトン類またはトルエン、 キシレン等の芳香族炭化水素などの有機溶剤単独または混合溶剤に固型 分濃度が 3〜10重量％になるように溶解して液状として調製される。  A vulcanized adhesive composition containing each of these components as an essential component can be prepared by adding each component to a ketone such as methyl ethyl ketone or methyl isobutyl ketone or an organic solvent such as toluene or an aromatic hydrocarbon such as xylene alone or a mixed solvent It is prepared as a liquid by dissolving it so that its concentration will be 3 to 10% by weight.
以上の各成分よりなる加硫接着剤組成物を用いての加硫接着は、 加硫: 接着剤組成物を軟鋼、 ステンレス鋼、 アルミニウム、 アルミニウムダイ キャスト、 黄銅、 亜鉛等の金属上、 一般には金属板上にこれを塗布し、 室温下で風乾させた後、 約 100〜200°Cで約 5〜30分間程度の乾燥を行い、 そこに未加硫の（水素化）ニトリルゴム配合物を接合させ、 （水素化〉ニト リルゴムの加硫温度である約 150〜200°Cで加圧加硫させることによって 行われる。 発明を実施するための最良の形態 Vulcanization bonding using a vulcanized adhesive composition comprising the above components is as follows: Vulcanization: The adhesive composition is a metal such as mild steel, stainless steel, aluminum, aluminum die cast, brass, zinc, etc. This is coated on a metal plate, air-dried at room temperature, and then dried at about 100 to 200 ° C. for about 5 to 30 minutes, and the uncured (hydrogenated) nitrile rubber composition is stored there. Bonding, (Hydrogenation) Nit It is carried out by pressure vulcanization at about 150 to 200 ° C., which is the vulcanization temperature of rill rubber. BEST MODE FOR CARRYING OUT THE INVENTION
次に、 実施例について本発明を説明する。 なお、 単位は重量部であり カツコ内の値は固形分重量部を示している。  The invention will now be described by way of example. The unit is part by weight, and the value in Katsuko shows the solid part by weight.
実施例 1  Example 1
フエノールキシレリン樹脂 143 (100) (明和化成製品 MR- 7800 固形分 70%)  Phenyl xylerin resin 143 (100) (Meiwa Chemical Products MR-7800 solid content 70%)
レゾール型フヱノール樹脂 67 (40) Resole type phenolic resin 67 (40)
(大日本ィンキ化学工業製品 AF- 2639L 固形分 60%) (Dainippon Kinki Chemical Products AF-2639L solid content 60%)
未加硫二トリルゴム（日本合成ゴム製品 N-237) 40 塩素化ポリエチレン 20  Unvulcanized nitril rubber (Japan Synthetic Rubber Products N-237) 40 Chlorinated polyethylene 20
(ダイソ一製品 Z- 200塩素含有量 67%)  (Diose one product Z- 200 chlorine content 67%)
メチノレエチノレケトン 1865  Methinore ethinole ketone 1865
1865 実施例 2'  1865 Example 2 '
フエノールキシレリン樹脂（MR-7800) 143 (100) タレゾール変性ノポラック型フエノール樹脂 20 (8) (大日本ィンキ化学工業製品 KA-1053L 固形分 40%)  Phenyl xylerin resin (MR-7800) 143 (100) Taresol modified nopolac type phenolic resin 20 (8) (Dainippon Ink and Chemicals, Inc. KA-1053L solid content 40%)
レゾール型フヱノ一ル榭脂（AF - 2639L) 53 (32) 未加硫-トリルゴム（N- 237) 40 塩素化ポリエチレン（Z-200) 20 メチルェチルケトン 1862 トルエン 1862 実施例 3 Resole type fatty acid resin (AF-2639 L) 53 (32) Unvulcanized-Tolyl rubber (N-237) 40 Chlorinated polyethylene (Z-200) 20 Methyl ethyl ketone 1862 Toluene 1862 Example 3
フヱノールビフヱニル樹脂 143 (100)Funil biphenyl resin 143 (100)
(明和化成製品 MR-7851 固形分 70%) (Meiwa Chemical Products MR-7851 70% solids)
レゾール型フエノール樹脂（AF - 2639L) 67 (40) 未加硫-トリルゴム (N-237) 40 塩素化ポリエチレン（Z- 200) 20 メチノレエチノレケトン 1865 Resole-type phenolic resin (AF-2639 L) 67 (40) Unvulcanized-Tolyl rubber (N-237) 40 Chlorinated polyethylene (Z- 200) 20 Methinoretinoleketone 1865
1865 実施例 4  1865 Example 4
フエノールビフェニル樹脂（MR- 7851) 143 (100) クレゾール変性ノボラック型フヱノール樹脂（KA-1053L) 20 (8) レゾール型フエノ一ル榭脂 (AF-2639L) 53 (32) 未加硫二トリルゴム（N- 237) 40 塩素化ポリエチレン（Z- 200) 20 メチルェチノレケトン 1862 Phenol biphenyl resin (MR-7851) 143 (100) Cresol-modified novolak type phenolic resin (KA-1053L) 20 (8) Resol type phenolic resin (AF-2639L) 53 (32) Unvulcanized Nitryl rubber (N -237) 40 Chlorinated polyethylene (Z- 200) 20 Methyl ethinole ketone 1862
1862 比較例 1  1862 Comparative Example 1
レゾール型フヱノール樹脂（AF- 2639L) 167 (100) 未加硫二トリルゴム（N- 237) 28 塩素化ポリエチレン（Z- 200) 14 メチルェチルケトン 916 トルエン 916 比較例 2 Resole type phenol resin (AF-2639L) 167 (100) Uncured 2 tolyl rubber (N-237) 28 Chlorinated polyethylene (Z- 200) 14 Methyl ethyl ketone 916 Toluene 916 Comparative example 2
レゾール型フヱノ一ル榭脂（AF - 2639L) 167 (100) クレゾールノボラック型エポキシ樹月 40  Resole-type hydrophobe resin (AF-2639L) 167 (100) Cresol novolac epoxy resin month 40
(大日本ィンキ化学工業製品ェピクロン N695)  (Dainippon Kinki Chemical Products Epiclon N695)
未加硫二トリルゴム（N- 237) 40 塩素化ポリエチレン（Z- 200) 20 メチノレエチノレケトン 1867 トノレェン 1867 比較例 3  Unvulcanized nitril rubber (N-237) 40 Chlorinated polyethylene (Z- 200) 20 Methinouretinole ketone 1867 Tonorene 1867 Comparative example 3
クレゾール変性ノボラック型フニノール樹脂（KA- 1053L) 250 (100) レゾール型フヱノ一ル榭脂（AF - 2639L) 167 (100) 未加硫二トリルゴム（N-237) 58 塩素化ポリエチレン（Z-200) 29 メチノレエチノレケトン 2618 トルエン 2618 比較例 4 .  Cresol-modified novolak-type funinol resin (KA-1053L) 250 (100) resol-type fatty acid resin (AF-2639L) 167 (100) unvulcanized nitril rubber (N-237) 58 chlorinated polyethylene (Z-200) 29 Methionine ethyl ketone 2618 toluene 2618 Comparative Example 4.
塩素系ゴムベース接着剤（ロードファーイース ト製品ケムロック 252X) 以上の各成分からなる実施例 1〜4および比較例 1〜4の加硫接着剤組成 物を、 リン酸亜鉛処理した軟鋼板上に塗布し、 室温条件下に 10分間放置 して風乾させた後、 150°Cの焼付温度で 10分間の焼付処理が行われた。 これらの加硫接着剤焼付軟鋼板に、 下記配合例 1〜3の未加硫水素化二 トリルゴムコンパウンド（単位は重量部である）を接合させ、 i80°C、 6分 間の加圧加硫が行われた。 得られた加硫接着物について、 初期接着性試 験、 耐水試験、 耐 PAG試験おょぴ耐フロン試験が行われた c 初期接着性試験： JIS K6256 90° 剥離試験 Chlorinated rubber-based adhesive (load-free paste product Chemlock 252X) The vulcanized adhesive compositions of Examples 1 to 4 and Comparative Examples 1 to 4 comprising the above components were coated on a zinc phosphate-treated mild steel sheet. After coating and air-drying at room temperature for 10 minutes, baking was performed at a baking temperature of 150 ° C. for 10 minutes. Unvulcanized hydrogenated nitrile rubber compounds (units are parts by weight) of the following combination examples 1 to 3 are joined to these vulcanized adhesive-baked soft steel plates, and a pressure of 80 ° C. for 6 minutes is applied. Sulfurization took place. Initial adhesion test of the obtained vulcanized adhesive Testing, Water resistance test, PAG resistance test, C Freon resistance test c Initial adhesion test: JIS K 6 256 90 ° peel test
耐水試験： JIS K6256 90° 剥離試験片を 80°Cの温水中に浸せきし、 100 時間後に剥離試験を実施 Water resistance test: Soak the JIS K 6 256 90 ° peel test specimen in warm water at 80 ° C and carry out the peel test 100 hours later.
B AG試験： JIS K6256 90° 剥離試験を 150°Cの PAG (ポリアルキレングリ コール）オイル中に浸せきし、 100時間後に剥離試験を実施 耐フロン試験：接着剤を塗布した JIS K6256 90° 剥離用の金属板上に 0.  B AG test: JIS K 6 256 90 ° peel test immersed in PAG (polyalkylene glycol) oil at 150 ° C. 100 hours later peel test performed Freon resistance test: adhesive coated JIS K 6 256 90 ° for peel 0. on the metal plate of
5廳厚みのゴムシートを加圧加硫成形して得られたサン プルを圧力容器中に入れ、 そこにフロンガス（R134a)を 注入し、 40°Cの環境下に 24時間放置後サンプルを取り出 し、 150°Cオーブン中で 1時間加熱し、 その際に接着界面 に発生したフロンガスによる発泡起点の数を力ゥント  A sample obtained by pressure-vulcanization molding a 5 廳 -thick rubber sheet is placed in a pressure vessel, fluorocarbon gas (R134a) is injected therein, and the sample is left for 24 hours under an environment of 40 ° C. And heated in a 150 ° C oven for 1 hour, at which time the number of fluorocarbon gas bubbles generated at the bonding interface was determined.
(水素化二トリルゴム配合例 1〜3) (Hydrogenated Nitrile rubber formulation examples 1 to 3)
配合例 1 配合例 2 配合例 3 Formulation example 1 Formulation example 2 Formulation example 3
HNBR (日本ゼオン製品 Zetpol2020 ； CN36%) 100 100 HNBR (Nippon Zeon Products Zetpol 2020; CN 36%) 100 100
讓 R ( // 1020 ； CN44%) 100讓 R (// 1020; CN 44%) 100
N990カーボンブラック 10 140 N 990 carbon black 10 140
SRFカーボンブラック 51 ホワイ トカーボン（比表面積 70mVg) 60 SRF carbon black 51 white carbon (specific surface area 70mVg) 60
酸化亜鉛 5 5 5 ステアリン酸 0. 5 0. 5 0. 5 ジフヱニルァミン系老化防止剤 1. 5 1. 5 0. 5 (大内新興製品ノクラック CD) Zinc oxide 5 5 5 Stearic acid 0. 5 0. 5 0. 5 Diphenylamine-based anti-aging agent 1. 5 1. 5 0. 5 (Ouchi emerging products Nocrac CD)
ィミダゾール系老化防止剤 1. 5 1. 5 2 (大内新興製品ノクラック MB) Imidazole-based anti-aging agent 1. 5 1. 5 2 (Ouchi Emerging Products Nocl MB)
1， 3-ジ（第 3プチルパーォキシイソプロピル） 10 10 10 ベンゼン (濃度 40%) (日本油脂製品べ口キシモン F40) 1, 3- Di (third ptyl peroxide isopropyl) 10 10 10 Benzene (40% concentration) (NOF Oil Products Beguchi Ximone F40)
アジピン酸系可塑剤（旭電化製品 RS107) 10 10 Adipic acid plasticizer (Asahi Electronics RS 107) 10 10
ビュルシラン化合物（日本ュニカー製品 A151) 2 Bull Silane Compound (Nippon Union Products A 151) 2
加工助剤（ヒュルス製品べステネマー 8012) 5 Processing aids (Hüls product Bestemer 8012) 5
得られた結果は、 次の表 1〜3に示される。 表 1 (配合例 1)  The obtained results are shown in the following Tables 1 to 3. Table 1 (Formulation example 1)
実施例 比較例  Example Comparative Example
2 3 4 2 3 4 2 3 4 2 3 4
〔初期接着性試験〕 Initial Adhesion Test
接着強度 (N/mm) 18. 8 18. 8 18. 6 18. 9 8. 8 6. 5 18. 8 18. 9 ゴム残率 （％) 100 100 100 100 10 0 100 100 Adhesive strength (N / mm) 18. 8 18. 8 18. 6 18. 9 8. 8 6. 5 18. 8 1 8. 9 Percent rubber remaining (%) 100 100 100 100 10 0 100 100
〔耐水試験〕 [Water resistance test]
接着強度 (N/mm) 18. 5 18. 5 18. 5 18. 5 - - 18. 5 10. 1 ゴム残率 （o/0) 100 100 100 100 - - 100 0Adhesive strength (N / mm) 18. 5 18. 5 18. 5 18. 5--18. 5 10. 1 Rubber residual ratio (o / 0 ) 100 100 100 100--100 0
〔耐 PAG試験〕 [PAG resistance test]
接着強度 (N/mm) 17. 5 17. 5 17. 5 17. 5 - - 17. 5 16. 5 ゴム残率 （％) 100 100 100 100 一 - 100 80 Adhesive strength (N / mm) 17. 5 17. 5 17. 5 17. 5--17. 5 16. 5 Residual rubber percentage (%) 100 100 100 100 1-100 80
〔耐フ口ン試験〕 [Fun test]
発泡数 20 表 2 (配合例 2)  Foam number 20 Table 2 (Formulation example 2)
実施例 比較例  Example Comparative Example
2 3 4 2 3 4 〔初期接着性〕 2 3 4 2 3 4 Initial adhesion
接着強度 (N/mm) 17.9 18.1 17.9 17.8 17.8 17.7 17.9 17.9 ゴム残率 （%) 100 100 100 100 100 100 100 100 Adhesive strength (N / mm) 17.9 18.1 17.9 17.8 17.8 17.8 17.9 17.9 Rubber remaining ratio (%) 100 100 100 100 100 100 100 100
〔耐水試験〕 [Water resistance test]
接着強度 (N/mm) 17.5 17.3 17.1 17.3 11.1 17.1 17.5 8.5 ゴム残率 （0/0) 100 95 100 90 20 70 70 0Adhesive strength (N / mm) 17.5 17.3 17.1 17.3 11.1 17.1 17.5 8.5 Rubber Retention (0/0) 100 95 100 90 20 70 70 0
〔耐 PAG試験〕 [PAG resistance test]
接着強度 (N/mm) 17.5 17.5 17.5 17.5 17.3 16.5 17.5 16.5 ゴム残率 （％) 100 100 100 100 100 90 100 70 〔耐フ口ン試験〕  Adhesive strength (N / mm) 17.5 17.5 17.5 17.5 17.3 16.5 17.5 16.5 Rubber residual ratio (%) 100 100 100 100 100 90 100 70 [Foun resistant test]
発泡数 ひ 15 表 3 (配合例 3)  Foam number 15 Table 3 (Formulation example 3)
実施例 比較例  Example Comparative Example
1 2 3 4 2 3 4 1 2 3 4 2 3 4
〔初期接着性〕 Initial adhesion
接着強度 (N/mm) 17.1 17.2 17.1 17.3 17.0 17.2 17.2 17.2 ゴム残率 （％) 100 100 100 100 100 100 100 100 Adhesive strength (N / mm) 17.1 17.2 17.1 17.3 17.0 17.2 17.2 17.2 Residual rubber percentage (%) 100 100 100 100 100 100 100 100
〔耐水試験〕 [Water resistance test]
接着強度 (N/ram) 16.9 16.8 16.9 16.9 14.5 15.9 15 6.5 ゴム残率 （o/0) 100 100 100 100 50 80 60 0Adhesive strength (N / ram) 16.9 16.8 16.9 16.9 14.5 15.9 15 6.5 Rubber residual ratio (o / 0 ) 100 100 100 100 50 80 60 0 0
〔耐 PAG試験〕 [PAG resistance test]
接着強度 (N/mm) 17 16.8 16.9 16.9 16.4 16.9 16.9 12 ゴム残率 （0） 100 100 100 100 90 100 100 60 Adhesive strength (N / mm) 17 16.8 16.9 16.9 16.4 16.9 16.9 12 Rubber residual ratio (0) 100 100 100 100 90 100 100 60
〔耐フ口ン試験〕 [Fun test]
発泡数 0 0 0 0 1 3 6 10 産業上の利用可能性 Foam number 0 0 0 0 1 3 6 10 Industrial applicability
本発明に係る加硫接着剤組成物は、 金属と（水素化）二トリルゴムとの 加硫接着に際し、 二トリル含量が 18〜48%の（水素化）ニトリルゴムに有 効に適用され、 さらにフロンガス、 ポリアルキレングリコ一ルまたは水 などに長時間浸せきした場合にもその接着性の低下が抑えられるといつ た効果を奏する。 この加硫接着剤組成物を用レ、て加硫接着された金属と (水素化） -トリルゴムとの複合シ ル部品は、 冷媒用シール等として有 効に用いられる。  The vulcanized adhesive composition according to the present invention is effectively applied to (hydrogenated) nitrile rubber having a 2 tolyl content of 18 to 48% in vulcanization bonding of metal and (hydrogenated) 2 tolyl rubber. Even if it is immersed in CFC gas, polyalkylene glycol or water for a long time, it is effective to suppress the decrease in adhesion. A composite seal component of a (hydrogenated) -tolyl rubber composited with a vulcanized adhesive composition and a vulcanized adhesive composition is effectively used as a seal for a refrigerant or the like.

Claims

請 求 の 範 囲 The scope of the claims
1 . フエノールキシレリン榭脂またはフエノールビフヱニル樹脂 100重 量部、 レゾール型フヱノール樹脂 10~1000重量部、 ノポラック型フエノ ール樹脂 0〜1000重量部、 未加硫の二トリルゴム 10〜1000重量部および 塩素化ポリエチレン 10〜500重量部を含有してなる加硫接着剤組成物。  1. 100 parts by weight of phenol xylerin resin or phenol biphenyl resin, 10 to 1000 parts by weight of resol type phenol resin, 0 to 1000 parts by weight of nopolac type phenol resin, 10 to 1000 weight of uncured 2 tolyl rubber Vulcanized adhesive composition comprising 10 parts by weight and 10 to 500 parts by weight of chlorinated polyethylene.
2 . 有機溶剤溶液として調製された請求項 1記載の加硫接着剤組成物。2. The vulcanized adhesive composition according to claim 1, which is prepared as an organic solvent solution.
3 . 金属と二トリルゴムまたは水素化二トリルゴムとの加硫接着に用い られる請求項 1または 2記載の加硫接着剤組成物。 3. The vulcanized adhesive composition according to claim 1 or 2, which is used for the vulcanization adhesion of a metal and a nitrile rubber or a hydrogenated nitrile rubber.
4 . 請求項 1または 2記載の加硫接着剤組成物を用いて加硫接着された 金属と-トリルゴムまたは水素化二トリルゴムとの複合シール部品。 4. A composite seal component of a metal and a tolyl rubber or a hydrogenated nitril rubber vulcanized and bonded using the vulcanized adhesive composition according to claim 1 or 2.
' 5 . 冷媒用シールとして用いられる請求項 4記載の複合シール部品。 The composite seal part according to claim 4, which is used as a seal for a refrigerant.
PCT/JP2003/010829 2003-08-27 2003-08-27 Vulcanizable adhesive composition WO2005023952A1 (en)

Priority Applications (5)

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PCT/JP2003/010829 WO2005023952A1 (en) 2003-08-27 2003-08-27 Vulcanizable adhesive composition
CNB038247003A CN1326965C (en) 2003-08-27 2003-08-27 Vulcanizable adhesive composition
EP20030816006 EP1659161B1 (en) 2003-08-27 2003-08-27 Vulcanizable adhesive composition
US10/506,490 US7247388B2 (en) 2003-08-27 2003-08-27 Vulcanizable adhesive composition
AU2003261749A AU2003261749A1 (en) 2003-08-27 2003-08-27 Vulcanizable adhesive composition

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US9925741B2 (en) * 2007-06-06 2018-03-27 Nok Corporation Acrylic rubber-metal composite
JP5778864B2 (en) * 2012-06-01 2015-09-16 株式会社Tkx Adhesive composition for resin bond wire saw and method for producing resin bond wire saw
JP6099535B2 (en) * 2013-09-26 2017-03-22 住友理工株式会社 Conductive roll and method for producing the same
CN112175257B (en) * 2020-07-27 2022-03-29 浙江中瑞橡胶高分子材料股份有限公司 Foamed wear-resistant rubber

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JPS63295691A (en) * 1987-05-26 1988-12-02 Nok Corp Vulcanizing adhesive compound and bonding method using the same
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JPH06306340A (en) * 1993-02-26 1994-11-01 Nok Corp Vulcanizable adhesive composition
JPH0748426A (en) * 1993-05-31 1995-02-21 Mitsui Toatsu Chem Inc Solid thermosetting resol resin, production and use thereof
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EP1659161B1 (en) 2011-11-23
CN1326965C (en) 2007-07-18
AU2003261749A1 (en) 2005-03-29
US20050215712A1 (en) 2005-09-29
EP1659161A1 (en) 2006-05-24
CN1694937A (en) 2005-11-09
US7247388B2 (en) 2007-07-24
EP1659161A4 (en) 2009-01-21

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